JP6092145B2 - Substrate with antibacterial layer, antibacterial sheet, radiation imaging device, touch panel - Google Patents

Substrate with antibacterial layer, antibacterial sheet, radiation imaging device, touch panel Download PDF

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JP6092145B2
JP6092145B2 JP2014070044A JP2014070044A JP6092145B2 JP 6092145 B2 JP6092145 B2 JP 6092145B2 JP 2014070044 A JP2014070044 A JP 2014070044A JP 2014070044 A JP2014070044 A JP 2014070044A JP 6092145 B2 JP6092145 B2 JP 6092145B2
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silver
antibacterial
antibacterial layer
extract
substrate
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JP2015189196A (en
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秀雄 永▲崎▼
秀雄 永▲崎▼
柴田　路宏
路宏 柴田
成行　書史
書史 成行
節子 白土
節子 白土
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Fujifilm Corp
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Priority to JP2014070044A priority Critical patent/JP6092145B2/en
Priority to PCT/JP2015/059464 priority patent/WO2015147206A1/en
Priority to CN201580016825.5A priority patent/CN106163802B/en
Priority to EP15768620.5A priority patent/EP3124237B1/en
Priority to TW104109899A priority patent/TW201536549A/en
Publication of JP2015189196A publication Critical patent/JP2015189196A/en
Priority to US15/277,724 priority patent/US10244763B2/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/728—Hydrophilic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Description

本発明は、抗菌層付き基材、抗菌シート、放射線撮影装置、タッチパネルに関する。   The present invention relates to a substrate with an antibacterial layer, an antibacterial sheet, a radiation imaging apparatus, and a touch panel.

各種製品・部材の表面には、目的に応じ加工が施され、各種機能が付与されることが多い。その中でも、近年、基材表面に抗菌層を設ける技術が注目を集めている。
例えば、医療現場で使われる医療装置は、複数の患者と連続的に接触するものが多い。また、タッチパネルの表面は不特定多数の操作者が直接指で触れるため、その表面に細菌等が繁殖していると病気に感染する恐れがある。そこで、各種装置の表面に抗菌層を設けることにより、細菌の増殖や、病気の感染のリスクを低減することが可能となる。
このような技術としては、例えば、特許文献１においては、銀を含有するリン酸複塩からなる抗菌剤を含む耐擦傷性皮膜と基材とからなる前面板が開示されている。 The surface of various products / members is processed according to the purpose and is often given various functions. Among them, in recent years, a technique for providing an antibacterial layer on the surface of a substrate has attracted attention.
For example, many medical devices used in the medical field continuously contact a plurality of patients. Moreover, since the surface of the touch panel is directly touched by an unspecified number of operators with fingers, there is a risk of infection with bacteria if bacteria or the like are propagated on the surface. Therefore, by providing an antibacterial layer on the surface of various devices, it is possible to reduce the risk of bacterial growth and disease infection.
As such a technique, for example, Patent Document 1 discloses a front plate made of a scratch-resistant film containing an antibacterial agent made of a double salt containing silver and a base material.

特開２００２−３３７２７７号公報JP 2002-337277 A

一方、近年、各種装置（例えば、医療装置、タッチパネル）の使用頻度をより高めるために、より短時間で抗菌作用を示すことが求められている。
また、抗菌層を有する基材は照明光や外光に長時間曝されるが、その際に抗菌層が変色しないことが求められる。例えば、タッチパネル表面の抗菌層が変色してしまうと、タッチパネルの視認性が低下するおそれがある。
つまり、耐光性に優れると共に、短時間で抗菌作用を示す抗菌層が求められている。
本発明者らは、特許文献１に記載の抗菌層付き基材について検討を行ったところ、上記要件を十分に満たすものではなく、さらなる改良が必要であった。 On the other hand, in recent years, in order to increase the frequency of use of various devices (for example, medical devices and touch panels), it is required to exhibit antibacterial action in a shorter time.
Moreover, although the base material which has an antibacterial layer is exposed to illumination light and external light for a long time, it is calculated | required that the antibacterial layer does not discolor in that case. For example, if the antibacterial layer on the surface of the touch panel is discolored, the visibility of the touch panel may be reduced.
That is, there is a demand for an antibacterial layer that has excellent light resistance and exhibits an antibacterial action in a short time.
When the present inventors examined the base material with an antibacterial layer of patent document 1, it did not fully satisfy | fill the said requirements but the further improvement was required.

本発明は、上記実情を鑑みて、耐光性に優れ、短時間で抗菌作用を示す抗菌層を備える抗菌層付き基材を提供することを目的とする。
また、本発明は、抗菌シート、並びに、上記抗菌層付き基材を備える放射線撮影装置およびタッチパネルを提供することも目的とする。 An object of this invention is to provide the base material with an antibacterial layer provided with the antibacterial layer which is excellent in light resistance and shows an antibacterial action in a short time in view of the said situation.
Another object of the present invention is to provide an antibacterial sheet, and a radiographic apparatus and a touch panel including the antibacterial layer-coated substrate.

本発明者らは、上記課題について鋭意検討した結果、以下の構成により上記課題が解決できることを見出した。   As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following configuration.

（１） 基材と、基材表面の少なくとも一部に配置された抗菌層とを有する、抗菌層付き基材であって、
抗菌層が、銀を含む抗菌剤を少なくとも１種含み、
後述する抽出試験で測定される単位面積当たりの銀イオン量が１５〜５０ｎｇ／ｃｍ２である、抗菌層付き基材。
（２） 抗菌層の表面の水接触角が４０°以下である、（１）に記載の抗菌層付き基材。
（３） 抗菌剤が、担体と、担体上に担持された銀とを含む銀担持担体である、（１）または（２）に記載の抗菌層付き基材。
（４） 抗菌層が親水性基を有するポリマーを含む、（１）〜（３）のいずれかに記載の抗菌層付き基材。
（５） 親水性基がポリオキシアルキレン基を含む、（４）に記載の抗菌層付き基材。
（６） 抗菌層が、親水性基を有するモノマー、および、銀を含む抗菌剤を少なくとも有する硬化性組成物に硬化処理を施して形成される、（１）〜（４）のいずれかに記載の抗菌層付き基材。
（７） 親水性基を有するモノマー中の親水性基が、ポリオキシアルキレン基を含む、（６）に記載の抗菌層付き基材。
（８） （１）〜（７）のいずれかに記載の抗菌層付き基材を表面に有する、放射線撮影装置。
（９） （１）〜（７）のいずれかに記載の抗菌層付き基材を表面に有する、タッチパネル。
（１０） 抗菌剤を含む抗菌シートであって、
抗菌剤が、銀を含む抗菌剤を少なくとも１種含み、
後述する抽出試験で測定される単位面積当たりの銀イオン量が１５〜５０ｎｇ／ｃｍ２である、抗菌シート。
（１１） 表面の水接触角が４０°以下である、（１０）に記載の抗菌シート。
（１２） 抗菌剤が、担体と、担体上に担持された銀とを含む銀担持担体である、（１０）または（１１）に記載の抗菌シート。
（１３） さらに、親水性基を有するポリマーを含む、（１０）〜（１２）のいずれかに記載の抗菌シート。
（１４） 親水性基がポリオキシアルキレン基を含む、（１３）に記載の抗菌シート。
（１５） 親水性基を有するモノマー、および、銀を含む抗菌剤を少なくとも有する硬化性組成物に硬化処理を施して形成される、（１０）〜（１４）のいずれかに記載の抗菌シート。
（１６） 親水性基を有するモノマー中の親水性基が、ポリオキシアルキレン基を含む、（１５）に記載の抗菌シート。 (1) A substrate with an antibacterial layer, comprising a substrate and an antibacterial layer disposed on at least a part of the surface of the substrate,
The antibacterial layer contains at least one antibacterial agent containing silver;
The base material with an antibacterial layer whose silver ion amount per unit area measured by the extraction test mentioned later is 15-50 ng / cm < 2 >.
(2) The substrate with an antibacterial layer according to (1), wherein a water contact angle on the surface of the antibacterial layer is 40 ° or less.
(3) The substrate with an antibacterial layer according to (1) or (2), wherein the antibacterial agent is a silver-carrying carrier comprising a carrier and silver supported on the carrier.
(4) The base material with an antibacterial layer according to any one of (1) to (3), wherein the antibacterial layer contains a polymer having a hydrophilic group.
(5) The substrate with an antibacterial layer according to (4), wherein the hydrophilic group contains a polyoxyalkylene group.
(6) The antibacterial layer is formed by performing a curing treatment on a curable composition having at least a monomer having a hydrophilic group and an antibacterial agent containing silver, according to any one of (1) to (4). Base material with antibacterial layer.
(7) The substrate with an antibacterial layer according to (6), wherein the hydrophilic group in the monomer having a hydrophilic group contains a polyoxyalkylene group.
(8) A radiographic apparatus having the antibacterial layer-coated substrate according to any one of (1) to (7) on the surface.
(9) A touch panel having the substrate with an antibacterial layer according to any one of (1) to (7) on the surface.
(10) An antibacterial sheet containing an antibacterial agent,
The antibacterial agent includes at least one antibacterial agent containing silver,
The antibacterial sheet whose silver ion amount per unit area measured by the extraction test mentioned later is 15-50 ng / cm < 2 >.
(11) The antibacterial sheet according to (10), wherein the surface water contact angle is 40 ° or less.
(12) The antibacterial sheet according to (10) or (11), wherein the antibacterial agent is a silver-carrying carrier containing a carrier and silver supported on the carrier.
(13) The antibacterial sheet according to any one of (10) to (12), further including a polymer having a hydrophilic group.
(14) The antibacterial sheet according to (13), wherein the hydrophilic group includes a polyoxyalkylene group.
(15) The antibacterial sheet according to any one of (10) to (14), which is formed by subjecting a curable composition having at least a monomer having a hydrophilic group and an antibacterial agent containing silver to a curing treatment.
(16) The antibacterial sheet according to (15), wherein the hydrophilic group in the monomer having a hydrophilic group contains a polyoxyalkylene group.

本発明によれば、耐光性に優れ、短時間で抗菌作用を示す抗菌層を備える抗菌層付き基材を提供することができる。
また、本発明によれば、抗菌シート、並びに、上記抗菌層付き基材を備える放射線撮影装置およびタッチパネルを提供することもできる。 ADVANTAGE OF THE INVENTION According to this invention, the base material with an antibacterial layer provided with the antibacterial layer which is excellent in light resistance and shows an antibacterial action in a short time can be provided.
Moreover, according to this invention, a radiography apparatus and a touch panel provided with an antibacterial sheet and the said base material with an antibacterial layer can also be provided.

本発明の抗菌層付き基材の一実施態様の断面図である。It is sectional drawing of one embodiment of the base material with an antibacterial layer of this invention.

以下に、本発明の抗菌層付き基材、抗菌シート、放射線撮影装置およびタッチパネルについて説明する。
なお、本明細書において「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Below, the base material with an antibacterial layer of the present invention, an antibacterial sheet, a radiography apparatus, and a touch panel are explained.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

本発明の特徴点の一つとしては、抗菌層からの銀イオンの溶出量を制御している点が挙げられる。具体的には、後述する抽出試験で使用される所定の抽出液への抗菌層からの銀イオンの溶出（抽出）量が所定値以上であれば、より短時間で抗菌作用が得られることを見出している。また、その溶出（抽出）量が所定値以下であれば、耐光性に優れることを見出している。
以下では、まず、本発明の抗菌層付き基材について詳述する。 One of the features of the present invention is that the amount of silver ions eluted from the antibacterial layer is controlled. Specifically, if the elution (extraction) amount of silver ions from the antibacterial layer into the predetermined extract used in the extraction test described later is greater than or equal to the predetermined value, the antibacterial effect can be obtained in a shorter time. Heading. Further, it has been found that if the elution (extraction) amount is not more than a predetermined value, the light resistance is excellent.
Below, the base material with an antibacterial layer of this invention is first explained in full detail.

図１は、本発明の抗菌層付き基材の一実施態様の断面図である。図１に示すように、抗菌層付き基材１０は、基材１２と、基材１２上に配置された抗菌層１４とを有する。なお、抗菌層１４は、基材１２の表面の少なくとも一部に配置されていればよい。
以下、各部材について詳述する。 FIG. 1 is a cross-sectional view of one embodiment of the substrate with an antibacterial layer of the present invention. As shown in FIG. 1, the substrate 10 with an antibacterial layer includes a substrate 12 and an antibacterial layer 14 disposed on the substrate 12. The antibacterial layer 14 may be disposed on at least a part of the surface of the substrate 12.
Hereinafter, each member will be described in detail.

＜基材＞
基材は、抗菌層を支持する役割を果たし、その種類は特に制限されない。また、基材は、後述するように各種装置の一部（例えば、前面板）を構成するものであってもよい。
基材の形状は特に制限されないが、板状、フィルム状、シート状、チューブ状、繊維状、粒子状などが挙げられる。また、後述する抗菌層が配置される基材表面は、平坦面でも、凹面でも、凸面でもよい。
基材を構成する材料は特に制限されず、例えば、金属、ガラス、セラミックス、プラスチック（樹脂）などが挙げられる。なかでも、取り扱い性の点から、プラスチックが好ましい。言い換えれば、樹脂基材が好ましい。 <Base material>
A base material plays the role which supports an antimicrobial layer, and the kind in particular is not restrict | limited. Further, the base material may constitute a part of various devices (for example, a front plate) as described later.
The shape of the substrate is not particularly limited, and examples thereof include a plate shape, a film shape, a sheet shape, a tube shape, a fiber shape, and a particle shape. Further, the substrate surface on which the antibacterial layer described later is disposed may be a flat surface, a concave surface, or a convex surface.
The material which comprises a base material in particular is not restrict | limited, For example, a metal, glass, ceramics, a plastic (resin) etc. are mentioned. Of these, plastic is preferable from the viewpoint of handleability. In other words, a resin base material is preferable.

＜抗菌層＞
抗菌層は、基材の表面の少なくとも一部に配置され、抗菌作用を有する層である。
抗菌層は、銀を含む抗菌剤を少なくとも１種含む。
銀を含む抗菌剤（以後、銀系抗菌剤とも称する）としては、銀（銀原子）が含まれていればよく、その種類は特に制限されない。また、銀の形態も特に制限されず、例えば、金属銀、銀イオン、銀塩（銀錯体を含む）など形態で含まれる。なお、本明細書では、銀錯体は銀塩の範囲に含まれる。 <Antimicrobial layer>
The antibacterial layer is a layer that is disposed on at least a part of the surface of the substrate and has an antibacterial action.
The antibacterial layer contains at least one antibacterial agent containing silver.
The antibacterial agent containing silver (hereinafter also referred to as a silver antibacterial agent) is not particularly limited as long as it contains silver (silver atoms). Further, the form of silver is not particularly limited, and includes, for example, metallic silver, silver ions, silver salts (including silver complexes) and the like. In addition, in this specification, a silver complex is contained in the range of silver salt.

なお、銀塩としては、例えば、酢酸銀、アセチルアセトン酸銀、アジ化銀、銀アセチリド、ヒ酸銀、安息香酸銀、フッ化水素銀、臭素酸銀、臭化銀、炭酸銀、塩化銀、塩素酸銀、クロム酸銀、クエン酸銀、シアン酸銀、シアン化銀、（ｃｉｓ，ｃｉｓ−１，５−シクロオクタジエン）−１，１，１，５，５，５−ヘキサフルオロアセチルアセトン酸銀、ジエチルジチオカルバミン酸銀、フッ化銀（Ｉ）、フッ化銀（ＩＩ）、７，７−ジメチル−１，１，１，２，２，３，３−ヘプタフルオロ−４，６−オクタンジオン酸銀、ヘキサフルオロアンチモン酸銀、ヘキサフルオロヒ酸銀、ヘキサフルオロリン酸銀、ヨウ素酸銀、ヨウ化銀、イソチオシアン酸銀、シアン化銀カリウム、乳酸銀、モリブデン酸銀、硝酸銀、亜硝酸銀、酸化銀（Ｉ）、酸化銀（ＩＩ）、シュウ酸銀、過塩素酸銀、ペルフルオロ酪酸銀、ペルフルオロプロピオン酸銀、過マンガン酸銀、過レニウム酸銀、リン酸銀、ピクリン酸銀一水和物、プロピオン酸銀、セレン酸銀、セレン化銀、亜セレン酸銀、スルファジアジン銀、硫酸銀、硫化銀、亜硫酸銀、テルル化銀、テトラフルオロ硼酸銀、テトラヨードムキュリウム酸銀、テトラタングステン酸銀、チオシアン酸銀、ｐ−トルエンスルホン酸銀、トリフルオロメタンスルホン酸銀、トリフルオロ酢酸銀およびバナジン酸銀等が挙げられる。
また、銀錯体の一例としては、ヒスチジン銀錯体、メチオニン銀錯体、システイン銀錯体、アスパラギン酸銀錯体、ピロリドンカルボン酸銀錯体、オキソテトラヒドロフランカルボン酸銀錯体またはイミダゾール銀錯体などが挙げられる。 Examples of silver salts include silver acetate, silver acetylacetonate, silver azide, silver acetylide, silver arsenate, silver benzoate, silver hydrogen fluoride, silver bromate, silver bromide, silver carbonate, silver chloride, Silver chlorate, silver chromate, silver citrate, silver cyanate, silver cyanide, (cis, cis-1,5-cyclooctadiene) -1,1,1,5,5,5-hexafluoroacetylacetonic acid Silver, silver diethyldithiocarbamate, silver fluoride (I), silver fluoride (II), 7,7-dimethyl-1,1,1,2,2,3,3-heptafluoro-4,6-octanedione Silver oxide, silver hexafluoroantimonate, silver hexafluoroarsenate, silver hexafluorophosphate, silver iodate, silver iodide, silver isothiocyanate, potassium silver cyanide, silver lactate, silver molybdate, silver nitrate, silver nitrite, Silver (I) oxide, acid Silver (II), silver oxalate, silver perchlorate, silver perfluorobutyrate, silver perfluoropropionate, silver permanganate, silver perrhenate, silver phosphate, silver picrate monohydrate, silver propionate, selenium Silver oxide, silver selenide, silver selenite, silver sulfadiazine, silver sulfate, silver sulfide, silver sulfite, silver telluride, silver tetrafluoroborate, silver tetraiodomucurate, silver tetratungstate, silver thiocyanate, p -Silver toluenesulfonate, silver trifluoromethanesulfonate, silver trifluoroacetate, silver vanadate and the like.
Examples of the silver complex include a histidine silver complex, a methionine silver complex, a cysteine silver complex, a silver aspartate complex, a silver pyrrolidone carboxylate complex, a silver oxotetrahydrofuran carboxylate complex, and an imidazole silver complex.

銀系抗菌剤としては、例えば、上記銀塩（銀錯体）などの有機系の抗菌剤と、後述する担体を含む無機系の抗菌剤が挙げられるが、その種類は特に制限されない。
銀系抗菌剤のなかでも、抗菌層の耐光性がより優れる、および／または、抗菌性がより優れる点（以後、単に「本発明の効果がより優れる点」とも称する）で、担体と、担体上に担持された銀とを含む銀担持担体が好ましい。
担体の種類は特に制限されず、リン酸亜鉛カルシウム、リン酸カルシウム、リン酸ジルコニウム、リン酸アルミニウム、ケイ酸カルシウム、活性炭、活性アルミナ、シリカゲル、ゼオライト、ヒドロキシアパタイト、リン酸ジルコニウム、リン酸チタン、チタン酸カリウム、含水酸化ビスマス、含水酸化ジルコニウム、ハイドロタルサイトなどが挙げられる。なお、ゼオライトとしては、例えば、チャバサイト、モルデナイト、エリオナイト、クリノプチロライト等の天然ゼオライト、Ａ型ゼオライト、Ｘ型ゼオライト、Ｙ型ゼオライト等の合成ゼオライトが挙げられる。
また、本発明の効果がより優れる点で、担体としては、いわゆるセラミックスが好ましい。
上記銀担持担体の平均粒径は特に制限されないが、本発明の効果がより優れる点で、０．１〜１０μｍが好ましく、０．１〜２μｍがより好ましい。なお、上記平均粒径は、顕微鏡により少なくとも１０個の任意の銀担持担体の直径を測定し、それらを算術平均した値である。 Examples of the silver antibacterial agent include organic antibacterial agents such as the above-described silver salts (silver complexes) and inorganic antibacterial agents containing a carrier to be described later, but the type is not particularly limited.
Among silver-based antibacterial agents, a carrier and a carrier in that the light resistance of the antibacterial layer is superior and / or the antibacterial property is superior (hereinafter, also simply referred to as “the effect of the present invention is more excellent”). A silver-supported carrier comprising silver supported thereon is preferred.
The type of carrier is not particularly limited, and zinc calcium phosphate, calcium phosphate, zirconium phosphate, aluminum phosphate, calcium silicate, activated carbon, activated alumina, silica gel, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, titanic acid Examples include potassium, hydrous bismuth, hydrous zirconium, and hydrotalcite. Examples of the zeolite include natural zeolite such as chabasite, mordenite, erionite, and clinoptilolite, and synthetic zeolite such as A-type zeolite, X-type zeolite, and Y-type zeolite.
Moreover, what is called ceramics is preferable as a support | carrier from the point which the effect of this invention is more excellent.
The average particle size of the silver-supported carrier is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.1 to 2 μm, from the viewpoint that the effect of the present invention is more excellent. The average particle diameter is a value obtained by measuring the diameters of at least 10 arbitrary silver-carrying carriers with a microscope and arithmetically averaging them.

銀系抗菌剤中における銀の含有量は特に制限されないが、例えば、上記銀担持担体の場合、銀の含有量は、銀担持担体全質量に対して、０．１〜１０質量％が好ましく、０．３〜５質量％がより好ましい。   The silver content in the silver antibacterial agent is not particularly limited. For example, in the case of the above-described silver-supported carrier, the silver content is preferably 0.1 to 10% by mass relative to the total mass of the silver-supported carrier, 0.3-5 mass% is more preferable.

抗菌層中における上記銀系抗菌剤の含有量は特に制限されないが、本発明の効果がより優れる点で、抗菌層全質量に対する銀の含有量が０．００１〜２０質量％（好ましくは、０．００１〜５質量％）となるように銀系抗菌剤を抗菌層に含有させることが好ましい。
また、銀系抗菌剤として有機系の抗菌剤を用いる場合は、抗菌剤の含有量は特に制限されないが、抗菌層の機械的強度がより優れ、本発明の効果がより優れる点で、抗菌層全質量に対して、１〜４質量％が好ましい。
さらに、銀系抗菌剤として無機系の抗菌剤を用いる場合は、抗菌剤の含有量は特に制限されないが、抗菌層の機械的強度がより優れ、本発明の効果がより優れる点で、抗菌層全質量に対して、０．００１〜１０質量％が好ましく、０．０１〜５質量％がより好ましい。 The content of the silver antibacterial agent in the antibacterial layer is not particularly limited, but the silver content with respect to the total mass of the antibacterial layer is 0.001 to 20% by mass (preferably 0%) in that the effect of the present invention is more excellent. 0.001 to 5% by mass), it is preferable to contain a silver antibacterial agent in the antibacterial layer.
In addition, when an organic antibacterial agent is used as the silver antibacterial agent, the content of the antibacterial agent is not particularly limited, but the antibacterial layer is more excellent in mechanical strength and the effect of the present invention. 1-4 mass% is preferable with respect to the total mass.
Further, when an inorganic antibacterial agent is used as the silver antibacterial agent, the content of the antibacterial agent is not particularly limited, but the antibacterial layer is more excellent in mechanical strength and the effect of the present invention. 0.001-10 mass% is preferable with respect to the total mass, and 0.01-5 mass% is more preferable.

抗菌層には、上記銀系抗菌剤以外の成分が含まれていてもよい。
例えば、抗菌層には、親水性基を有するポリマー（以後、単に「親水性ポリマー」とも称する）が含まれていてもよい。抗菌層に親水性ポリマーが含まれることにより、抗菌層がより親水性を示し、水などを用いた洗浄により抗菌層上に付着した汚染物質をより容易に除去することが可能となる。
親水性基の種類は特に制限されず、例えば、ポリオキシアルキレン基（例えば、ポリオキシエチレン基、ポリオキシプロピレン基、オキシエチレン基とオキシプロピレン基がブロックまたはランダム結合したポリオキシアルキレン基)、アミノ基、カルボキシル基、カルボキシル基のアルカリ金属塩、ヒドロキシ基、アルコキシ基、アミド基、カルバモイル基、スルホンアミド基、スルファモイル基、スルホン酸基、スルホン酸基のアルカリ金属塩などが挙げられる。なかでも、本発明の効果がより優れる点で、ポリオキシアルキレン基が好ましい。
親水性ポリマーの主鎖の構造は特に制限されず、例えば、ポリウレタン、ポリ（メタ）アクリレート、ポリスチレン、ポリエステル、ポリアミド、ポリイミド、ポリウレアなどが挙げられる。
なお、ポリ（メタ）アクリレートとは、ポリアクリレートおよびポリメタクリレートの両方を含む概念である。 The antibacterial layer may contain components other than the silver antibacterial agent.
For example, the antibacterial layer may contain a polymer having a hydrophilic group (hereinafter, also simply referred to as “hydrophilic polymer”). By including a hydrophilic polymer in the antibacterial layer, the antibacterial layer is more hydrophilic, and contaminants attached to the antibacterial layer can be more easily removed by washing with water or the like.
The type of the hydrophilic group is not particularly limited, and examples thereof include polyoxyalkylene groups (for example, polyoxyethylene groups, polyoxypropylene groups, polyoxyalkylene groups in which oxyethylene groups and oxypropylene groups are blocked or randomly bonded), amino Group, carboxyl group, alkali metal salt of carboxyl group, hydroxy group, alkoxy group, amide group, carbamoyl group, sulfonamide group, sulfamoyl group, sulfonic acid group, alkali metal salt of sulfonic acid group and the like. Among these, a polyoxyalkylene group is preferable in that the effect of the present invention is more excellent.
The structure of the main chain of the hydrophilic polymer is not particularly limited, and examples thereof include polyurethane, poly (meth) acrylate, polystyrene, polyester, polyamide, polyimide, and polyurea.
Poly (meth) acrylate is a concept including both polyacrylate and polymethacrylate.

親水性ポリマーの好適態様の一つとしては、上記親水性基を有するモノマー（以後、単に「親水性モノマー」とも称する）を重合させて得られるポリマーが挙げられる。
親水性モノマーとは、上記親水性基と重合性基とを有する化合物を意図する。親水性基の定義は上述の通りである。
親水性モノマー中における親水性基の数は特に制限されないが、抗菌層がより親水性を示す点より、２個以上が好ましく、２〜６個がより好ましく、２〜３個がさらに好ましい。 One preferred embodiment of the hydrophilic polymer is a polymer obtained by polymerizing the monomer having the hydrophilic group (hereinafter, also simply referred to as “hydrophilic monomer”).
A hydrophilic monomer intends the compound which has the said hydrophilic group and polymeric group. The definition of the hydrophilic group is as described above.
The number of hydrophilic groups in the hydrophilic monomer is not particularly limited, but is preferably 2 or more, more preferably 2 to 6 and even more preferably 2 to 3 from the point that the antibacterial layer is more hydrophilic.

重合性基の種類は特に制限されず、例えば、ラジカル重合性基、カチオン重合性基、アニオン重合性基などが挙げられる。ラジカル重合性基としては、（メタ）アクリロイル基、アクリルアミド基、ビニル基、スチリル基、アリル基などが挙げられる。カチオン重合性基としては、ビニルエーテル基、オキシラニル基、オキセタニル基などが挙げられる。なかでも、（メタ）アクリロイル基が好ましい。
なお、（メタ）アクリロイル基とは、アクリロイル基およびメタアクリロイル基の両方を含む概念である。
親水性モノマー中における重合性基の数は特に制限されないが、得られる抗菌層の機械的強度がより優れる点で、２個以上が好ましく、２〜６個がより好ましく、２〜３個がさらに好ましい。 The kind of the polymerizable group is not particularly limited, and examples thereof include a radical polymerizable group, a cationic polymerizable group, and an anion polymerizable group. Examples of the radical polymerizable group include (meth) acryloyl group, acrylamide group, vinyl group, styryl group, allyl group and the like. Examples of the cationic polymerizable group include a vinyl ether group, an oxiranyl group, and an oxetanyl group. Of these, a (meth) acryloyl group is preferable.
The (meth) acryloyl group is a concept including both an acryloyl group and a methacryloyl group.
The number of polymerizable groups in the hydrophilic monomer is not particularly limited, but is preferably 2 or more, more preferably 2 to 6, more preferably 2 to 3 in terms of more excellent mechanical strength of the obtained antibacterial layer. preferable.

親水性モノマーの好適態様の一つとしては、以下の式（１）で表される化合物が挙げられる。   One preferred embodiment of the hydrophilic monomer is a compound represented by the following formula (1).

式（１）中、Ｒ１は、置換基を表す。置換基の種類は特に制限されず、公知の置換基が挙げられ、例えば、ヘテロ原子を有していてもよい炭化水素基（例えば、アルキル基、アリール基）、上記親水性基などが挙げられる。
Ｒ２は、重合性基を表す。重合性基の定義は上述の通りである。
Ｌ１は、単結合または２価の連結基を表す。２価の連結基の種類は特に制限されず、例えば、−Ｏ−、−ＣＯ−、−ＮＨ−、−ＣＯ−ＮＨ−、−ＣＯＯ−、−Ｏ−ＣＯＯ−、アルキレン基、アリーレン基、ヘテロアリール基、および、それらの組み合わせが挙げられる。
Ｌ２は、ポリオキシアルキレン基を表す。ポリオキシアルキレン基とは、以下の式（２）で表される基を意図する。
式（２） ＊−（ＯＲ３）ｍ−＊
式（２）中、Ｒ３は、アルキレン基（例えば、エチレン基、プロピレン基）を表す。ｍは、２以上の整数を表し、２〜１０が好ましく、２〜６がより好ましい。なお、＊は、結合位置を表す。
ｎは、１〜４の整数を表す。 In formula (1), R 1 represents a substituent. The type of the substituent is not particularly limited, and examples thereof include known substituents. Examples thereof include a hydrocarbon group (for example, an alkyl group or an aryl group) that may have a hetero atom, and the above hydrophilic group. .
R 2 represents a polymerizable group. The definition of the polymerizable group is as described above.
L 1 represents a single bond or a divalent linking group. The type of the divalent linking group is not particularly limited. For example, -O-, -CO-, -NH-, -CO-NH-, -COO-, -O-COO-, an alkylene group, an arylene group, a hetero group Aryl groups and combinations thereof are mentioned.
L 2 represents a polyoxyalkylene group. The polyoxyalkylene group intends a group represented by the following formula (2).
Formula (2) *-(OR < 3 >) m- *
In formula (2), R 3 represents an alkylene group (for example, an ethylene group or a propylene group). m represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. Note that * represents a binding position.
n represents an integer of 1 to 4.

親水性モノマーの具体例としては、ポリオキシアルキレン変性ペンタエリスリトールトリアクリレート、ポリオキシアルキレン変性ビスフェノールＡジアクリレートが挙げられる。   Specific examples of the hydrophilic monomer include polyoxyalkylene-modified pentaerythritol triacrylate and polyoxyalkylene-modified bisphenol A diacrylate.

親水性ポリマーを得る際には、上記親水性モノマーと他のモノマー（親水性基を含まないモノマー）とを併用してもよい。つまり、親水性モノマーと、他のモノマー（親水性モノマー以外のモノマー）とを共重合させて得られる親水性ポリマーを使用してもよい。
他のモノマーの種類は特に制限されず、重合性基を有する公知のモノマーであれば適宜使用できる。重合性基の定義は、上述の通りである。
なかでも、抗菌層の機械的強度がより優れる点で、重合性基を２以上有する多官能モノマーが好ましい。多官能モノマーは、いわゆる架橋剤として作用する。
多官能モノマー中に含まれる重合性基の数は特に制限されず、抗菌層の機械的強度がより優れる点、および、取扱い性の点から、２〜１０個が好ましく、２〜６個がより好ましい。
多官能モノマーとしては、例えば、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラアクリレートが挙げられる。 When obtaining a hydrophilic polymer, the above hydrophilic monomer and another monomer (a monomer not containing a hydrophilic group) may be used in combination. That is, you may use the hydrophilic polymer obtained by copolymerizing a hydrophilic monomer and another monomer (monomer other than a hydrophilic monomer).
The kind of other monomer is not particularly limited, and any known monomer having a polymerizable group can be used as appropriate. The definition of the polymerizable group is as described above.
Among these, a polyfunctional monomer having two or more polymerizable groups is preferable in that the mechanical strength of the antibacterial layer is more excellent. The polyfunctional monomer acts as a so-called crosslinking agent.
The number of polymerizable groups contained in the polyfunctional monomer is not particularly limited, and is preferably 2 to 10 and more preferably 2 to 6 from the viewpoint of better mechanical strength of the antibacterial layer and handleability. preferable.
Examples of the polyfunctional monomer include trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate, and pentaerythritol tetraacrylate.

親水性モノマーと他のモノマー（特に、多官能モノマー）との混合比（親水性モノマーの質量／他のモノマーの質量）は特に制限されないが、抗菌層の親水性の制御がしやすい点から、０．０１〜１０が好ましく、０．１〜１０がより好ましい。   The mixing ratio (mass of hydrophilic monomer / mass of other monomer) between the hydrophilic monomer and other monomer (especially polyfunctional monomer) is not particularly limited, but from the point that it is easy to control the hydrophilicity of the antibacterial layer, 0.01-10 are preferable and 0.1-10 are more preferable.

なお、抗菌層中における上記親水性ポリマーの含有量は特に制限されないが、抗菌層上の汚染物質の洗浄による除去性がより優れる点で、抗菌層全質量に対して、５０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上がさらに好ましい。   The content of the hydrophilic polymer in the antibacterial layer is not particularly limited, but is preferably 50% by mass or more with respect to the total mass of the antibacterial layer in terms of more excellent removability of the contaminant on the antibacterial layer 70 mass% or more is more preferable, and 90 mass% or more is further more preferable.

（抗菌層の製造方法）
抗菌層の製造方法は特に制限されず、公知の方法が採用できる。例えば、上述した銀系抗菌剤を含む組成物を基材上に塗布して抗菌層を形成する方法や、別途作製した銀系抗菌剤を含む抗菌シートを基材上の所定の位置に貼り付ける方法などが挙げられる。
なかでも、抗菌層の厚みや表面凹凸の調整がより容易である点から、上述した、親水性モノマーおよび銀系抗菌剤を含む組成物（硬化性組成物）を基材上の所定の位置に塗布して塗膜を形成し、塗膜に硬化処理を施すことにより抗菌層を形成する方法（塗布法）が好ましい。 (Production method of antibacterial layer)
The production method of the antibacterial layer is not particularly limited, and a known method can be adopted. For example, a method of forming the antibacterial layer by applying the above-described composition containing a silver antibacterial agent on a substrate, or affixing a separately prepared antibacterial sheet containing a silver antibacterial agent to a predetermined position on the substrate The method etc. are mentioned.
Among these, the composition (curable composition) containing the hydrophilic monomer and the silver-based antibacterial agent described above is placed at a predetermined position on the base material because it is easier to adjust the thickness of the antibacterial layer and the surface unevenness. A method (coating method) in which an antibacterial layer is formed by coating to form a coating film and subjecting the coating film to a curing treatment is preferable.

組成物には、例えば、上述した親水性モノマーおよび銀系抗菌剤が含まれるが、他の成分（上記他のモノマー、滑剤、溶媒（水または有機溶媒））が含まれていてもよい。
なお、組成物には、重合開始剤が含まれていてもよい。重合開始剤が含まれることにより、塗膜中での重合がより効率よく進行し、機械的強度に優れる抗菌層が形成される。重合開始剤の種類は特に制限されず、硬化処理の方法により最適な種類が選択されるが、例えば、熱重合開始剤、光重合開始剤が選択される。より具体的には、ベンゾフェノン、フェニルフォスフィンオキシドなどの芳香族ケトン類、α−ヒドロキシアルキルフェノン系化合物（ＢＡＳＦ ＩＲＧＡＣＵＲＥ１８４、１２７、２９５９、ＤＡＲＯＣＵＲ１１７３など)、フェニルフォスフィンオキシド系化合物（ＭＡＰＯ：ＢＡＳＦ ＬＵＣＩＲＩＮ ＴＰＯ、ＢＡＰＯ：ＢＡＳＦ ＩＲＧＡＣＵＲＥ ８１９）などが挙げられる。
組成物中に含まれる重合開始剤の含有量は特に制限されないが、親水性モノマーおよび他のモノマーの合計質量１００質量部に対して、０．１〜１５質量部が好ましく、１〜６質量部がより好ましい。 The composition includes, for example, the above-described hydrophilic monomer and silver-based antibacterial agent, but may include other components (the above-mentioned other monomer, lubricant, solvent (water or organic solvent)).
The composition may contain a polymerization initiator. By including the polymerization initiator, the polymerization in the coating proceeds more efficiently, and an antibacterial layer having excellent mechanical strength is formed. The type of the polymerization initiator is not particularly limited, and an optimal type is selected depending on the method of the curing treatment. For example, a thermal polymerization initiator and a photopolymerization initiator are selected. More specifically, aromatic ketones such as benzophenone and phenylphosphine oxide, α-hydroxyalkylphenone compounds (BASF IRGACURE184, 127, 2959, DAROCUR1173, etc.), phenylphosphine oxide compounds (MAPO: BASF LUCIRIN TPO) , BAPO: BASF IRGACURE 819).
Although content in particular of the polymerization initiator contained in a composition is not restrict | limited, 0.1-15 mass parts is preferable with respect to 100 mass parts of total mass of a hydrophilic monomer and another monomer, 1-6 mass parts Is more preferable.

組成物を塗布する方法は特に制限されず、公知の塗布方法が採用される。
また、硬化処理の方法は特に制限されず、加熱処理または光照射処理が挙げられる。 The method for applying the composition is not particularly limited, and a known application method is employed.
Moreover, the method of a hardening process is not restrict | limited in particular, A heat processing or a light irradiation process is mentioned.

（抗菌層の特性）
抗菌層の平均厚みは特に制限されないが、機械的特性および抗菌性の点からは、０．５〜２０μｍが好ましく、１〜１０μｍがより好ましい。
なお、抗菌層の平均厚みの測定方法としては、抗菌層のサンプル片を樹脂に包埋して、ミクロトームで断面を削り出し、削り出した断面を走査電子顕微鏡で観察し測定する。抗菌層の任意の１０点の位置における厚みを測定し、それらを算術平均する。 (Characteristics of antibacterial layer)
The average thickness of the antibacterial layer is not particularly limited, but is preferably 0.5 to 20 μm and more preferably 1 to 10 μm from the viewpoint of mechanical properties and antibacterial properties.
In addition, as a measuring method of the average thickness of the antibacterial layer, a sample piece of the antibacterial layer is embedded in a resin, a cross section is cut out with a microtome, and the cut out cross section is observed and measured with a scanning electron microscope. The thickness at any 10 positions of the antibacterial layer is measured, and they are arithmetically averaged.

抗菌層の表面の水接触角は特に制限されないが、洗浄などによる抗菌層上の汚染物質の除去性がより優れ、抗菌性がより優れる点で、４０°以下が好ましく、３０°以下がより好ましく、２５°以下がさらに好ましい。下限は特に制限されないが、使用される材料特性の点から、５°以上の場合が多い。
なお、本明細書において、水接触角は、ＪＩＳ Ｒ ３２５７：１９９９の静滴法に基づいて測定を行う。測定には、株式会社ニック製ＬＳＥ-ＭＥ１（ソフトウェア２ｗｉｎ ｍｉｎｉ）を用いる。より具体的には、純水を用いて室温２０℃で、水平を保った抗菌層表面上に液滴２μｌを滴下し、滴下後２０秒時点での接触角を測定する。 The water contact angle on the surface of the antibacterial layer is not particularly limited, but is preferably 40 ° or less, more preferably 30 ° or less, in terms of better removal of contaminants on the antibacterial layer by washing or the like and better antibacterial properties. 25 ° or less is more preferable. Although a minimum in particular is not restrict | limited, From the point of the material characteristic to be used, it is often 5 degrees or more.
In addition, in this specification, a water contact angle is measured based on the sessile drop method of JISR3257: 1999. For the measurement, LSE-ME1 (software 2win mini) manufactured by Nick Co., Ltd. is used. More specifically, 2 μl of a droplet is dropped on the surface of the antibacterial layer kept horizontal at room temperature of 20 ° C. using pure water, and the contact angle at 20 seconds after the dropping is measured.

＜抗菌層付き基材＞
上記で述べた基材と抗菌層とを備える抗菌層付き基材は、後述する抽出試験で測定される単位面積当たりの銀イオン量が１５〜５０ｎｇ／ｃｍ２を示し、本発明の効果がより優れる点で、１５〜４０ｎｇ／ｃｍ２が好ましく、１５〜３０ｎｇ／ｃｍ２がより好ましい。
上記銀イオン量が１５ｎｇ／ｃｍ２未満の場合、抗菌性に劣る。銀イオン量が５０ｎｇ／ｃｍ２超の場合、耐光性に劣る。 <Base material with antibacterial layer>
The base material with an antibacterial layer comprising the base material and the antibacterial layer described above shows a silver ion amount per unit area of 15 to 50 ng / cm 2 measured by an extraction test described later, and the effect of the present invention is more effective. In the point which is excellent, 15-40 ng / cm < 2 > is preferable and 15-30 ng / cm < 2 > is more preferable.
When the said silver ion amount is less than 15 ng / cm < 2 >, it is inferior to antibacterial property. When the amount of silver ions exceeds 50 ng / cm 2 , the light resistance is poor.

以下、抽出試験の方法について詳述する。
抽出試験では、ＪＩＳ Ｚ ２８０１：２０１０に規定された１／５００普通ブイヨン培地を抽出液として用いる。この抽出液の温度を３５±１℃に制御して、抗菌層付き基材中の抗菌層（抗菌層の面積：４ｃｍ２（２ｃｍ×２ｃｍ））と抽出液（液量：９ｍＬ）とを１時間接触させる。なお、抗菌層と抽出液とを接触させる方法としては、抽出液中に抗菌層付き基材を浸漬する方法が実施される。
次に、１時間終了後、抽出液から抗菌層付き基材を回収して、抽出液に抽出された銀イオン量（ｎｇ）を測定する。抽出液中の銀イオン量の測定は、原子吸光分析（イエナ製ｃｏｎｔｒＡＡ７００）を用いて実施し、あらかじめ作成した検量線より銀イオン量を求める。
なお、銀イオン量を測定する際には、必要に応じて、測定の安定性を高めるため、抽出液に硝酸（約１ｍＬ）を加えることが好ましい。 Hereinafter, the extraction test method will be described in detail.
In the extraction test, 1/500 ordinary bouillon medium defined in JIS Z 2801: 2010 is used as the extract. By controlling the temperature of this extract to 35 ± 1 ° C., the antibacterial layer (antibacterial layer area: 4 cm 2 (2 cm × 2 cm)) and the extract (liquid amount: 9 mL) in the substrate with the antibacterial layer are 1 Contact for hours. In addition, as a method of making an antibacterial layer and an extract liquid contact, the method of immersing a base material with an antibacterial layer in an extract is implemented.
Next, after the completion of one hour, the base material with the antibacterial layer is recovered from the extract, and the amount of silver ions (ng) extracted in the extract is measured. The amount of silver ions in the extract is measured using atomic absorption analysis (contrAA700 manufactured by Jena), and the amount of silver ions is obtained from a calibration curve prepared in advance.
In addition, when measuring the amount of silver ions, it is preferable to add nitric acid (about 1 mL) to the extract as necessary in order to improve the measurement stability.

次に、得られた銀イオン量を、抗菌層の抽出液との接触面積（４ｃｍ２）で除して、単位面積当たりの銀イオン量（ｎｇ／ｃｍ２）を算出する。抗菌層の抽出液との接触面積とは、抗菌層と抽出液とを接触させた際に抗菌層表面の抽出液と接触していた面積を意図し、例えば、図１においては抗菌層１４の基材１２側とは反対側の主面１４ａの面積を意図する。
この得られた銀イオン量は、抗菌層からの銀イオンの溶出（抽出）の程度を表している。 Next, the silver ion amount (ng / cm 2 ) per unit area is calculated by dividing the obtained silver ion amount by the contact area (4 cm 2 ) with the antibacterial layer extract. The contact area of the antibacterial layer with the extract is intended to mean the area in contact with the extract on the surface of the antibacterial layer when the antibacterial layer and the extract are brought into contact. The area of the main surface 14a opposite to the substrate 12 side is intended.
The obtained silver ion amount represents the degree of elution (extraction) of silver ions from the antibacterial layer.

上記抗菌層付き基材は、種々の用途に適用することができ、種々の装置の表面に配置することができる。この抗菌層付き基材が表面に配置された装置は、優れた耐光性、および、短時間での抗菌性が得られる。
抗菌層付き基材が適用される装置としては、例えば、放射線撮影装置、タッチパネルなどが挙げられる。 The said base material with an antibacterial layer can be applied to various uses, and can be arrange | positioned on the surface of a various apparatus. An apparatus in which the substrate with the antibacterial layer is disposed on the surface can provide excellent light resistance and antibacterial properties in a short time.
Examples of the device to which the substrate with the antibacterial layer is applied include a radiation imaging device and a touch panel.

なお、上述した抗菌層は、それ自体を抗菌シートとして使用することもできる。抗菌シートの構成は上述した抗菌層と同じであり、上記抽出試験も抗菌層の代わりに抗菌シートを用いて実施される。つまり、上述した所定の抽出液と抗菌シートとを接触させ、抽出液に抽出された銀イオン量を測定し、得られた値を抗菌シートの抽出液との接触面積で除して、得られた単位面積当たりの銀イオン量が、上述した所定の範囲であればよい。   In addition, the antibacterial layer mentioned above can also be used as an antibacterial sheet itself. The configuration of the antibacterial sheet is the same as that of the antibacterial layer described above, and the extraction test is also performed using an antibacterial sheet instead of the antibacterial layer. That is, it is obtained by bringing the above-mentioned predetermined extract into contact with the antibacterial sheet, measuring the amount of silver ions extracted into the extract, and dividing the obtained value by the contact area with the extract of the antibacterial sheet. The amount of silver ions per unit area may be within the predetermined range described above.

以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

（硬化性組成物の調製）
以下に示す各成分を混合して、硬化性組成物を調製した。
親水性モノマー：Ｍｉｒａｍｅｒ Ｍ４００４（東洋ケミカルズ社製） ７６質量部
架橋剤：Ａ-ＤＰＨ（新中村化学工業株式会社製） ２１質量部
重合開始剤：ＩＲＧＡＣＵＲＥ（ＢＡＳＦ社製） ３質量部
溶剤成分（その１）：メチルアルコール １５質量部
溶剤成分（その２）：プロピレングリコールモノメチルエーテル ３５質量部 (Preparation of curable composition)
Each component shown below was mixed and the curable composition was prepared.
Hydrophilic monomer: Miramer M4004 (manufactured by Toyo Chemicals) 76 parts by mass Crosslinking agent: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) 21 parts by mass Polymerization initiator: IRGACURE (manufactured by BASF) 3 parts by mass of solvent component 1): 15 parts by mass of methyl alcohol Solvent component (2): 35 parts by mass of propylene glycol monomethyl ether

＜実施例および比較例＞
上記で調製された硬化性組成物中に表１に示す割合に従って、銀セラミックス粒子分散液（富士ケミカル社製、平均粒径０．８μｍ）を添加して混合し、抗菌層形成用の硬化性組成物を調製した。
得られた抗菌層形成用の硬化性組成物を、ポリカーボネートシート（旭硝子製カーボグラスＣＦＲ１１０Ｃ）に表１に示す厚みの抗菌層が得られるように塗布し、６０℃で３０分乾燥させたあと、ＵＶ照射によりモノマーを硬化させることで、抗菌層を形成し、評価サンプル（抗菌層付き基材）を作製した。
なお、実施例６では、親水性モノマーと架橋剤との質量比を制御して、所定の水接触角となるようにした。 <Examples and Comparative Examples>
In accordance with the ratio shown in Table 1 in the curable composition prepared above, a silver ceramic particle dispersion (manufactured by Fuji Chemical Co., Ltd., average particle size 0.8 μm) is added and mixed to form a curable composition for forming an antibacterial layer. A composition was prepared.
The obtained antibacterial layer-forming curable composition was applied to a polycarbonate sheet (Carboglass CFR110C manufactured by Asahi Glass Co., Ltd.) so that the antibacterial layer having the thickness shown in Table 1 was obtained, and dried at 60 ° C for 30 minutes. By curing the monomer by UV irradiation, an antibacterial layer was formed, and an evaluation sample (substrate with an antibacterial layer) was produced.
In Example 6, the mass ratio between the hydrophilic monomer and the crosslinking agent was controlled so that the predetermined water contact angle was obtained.

＜評価＞
得られた実施例および比較例の評価サンプルを用いて、以下の評価を行った。結果は表１にまとめて示す。
（抗菌性評価方法）
抗菌性評価は、ＪＩＳ Ｚ ２８０１：２０１０に記載の評価方法に準拠し、菌液への接触時間２４時間を１時間に変更して試験を実施した。それぞれの試験後の菌数（個／ｃｍ2）を測定し、以下の基準に従って評価を行った。菌種は大腸菌を用いた。実用上、「Ａ」、「Ｂ」が好ましい。
「Ａ」：菌数が５個／ｃｍ2未満
「Ｂ」：菌数が５個／ｃｍ2以上１０個／ｃｍ2未満
「Ｃ」：菌数が１０個／ｃｍ2以上 <Evaluation>
The following evaluation was performed using the evaluation samples of the obtained Examples and Comparative Examples. The results are summarized in Table 1.
(Antimicrobial evaluation method)
The antibacterial evaluation was performed in accordance with the evaluation method described in JIS Z 2801: 2010 by changing the contact time to the bacterial solution from 24 hours to 1 hour. The number of bacteria (cells / cm 2 ) after each test was measured and evaluated according to the following criteria. E. coli was used as the bacterial species. Practically, “A” and “B” are preferable.
“A”: the number of bacteria is less than 5 / cm 2 “B”: the number of bacteria is 5 / cm 2 or more and less than 10 / cm 2 “C”: the number of bacteria is 10 / cm 2 or more

（耐光性試験）
キセノンウェザオメーター（スガ試験機製）にて出力６０Ｗ／ｍ2で１０時間照射後の評価サンプル中の抗菌層の変色を、目視にて以下の観点で評価した。実用上、「Ａ」が好ましい。
「Ａ」：変色なし
「Ｂ」：変色あり (Light resistance test)
Discoloration of the antibacterial layer in the evaluation sample after irradiation for 10 hours at an output of 60 W / m 2 with a xenon weatherometer (manufactured by Suga Test Instruments) was visually evaluated from the following viewpoints. Practically, “A” is preferable.
“A”: No color change “B”: Color change

また、各実施例および比較例にて得られた評価サンプルを用いて、上述した抽出試験を実施した。
また、各実施例および比較例にて得られた評価サンプル中の抗菌層の水接触角を上述した方法にて測定した。結果を表１に示す。 Moreover, the extraction test mentioned above was implemented using the evaluation sample obtained by each Example and the comparative example.
Moreover, the water contact angle of the antibacterial layer in the evaluation samples obtained in the respective examples and comparative examples was measured by the method described above. The results are shown in Table 1.

表１中、「抗菌剤の質量（質量％）」は、抗菌層中の硬化物成分の質量（硬化性組成物中の全固形分質量）に対する抗菌剤の含有量（質量％）を意図する。
表１中、「Ａｇイオン量」欄は、抽出試験で測定される単位面積当たりの銀イオン量を意図する。 In Table 1, “mass (% by mass) of antibacterial agent” intends the content (% by mass) of the antibacterial agent with respect to the mass of the cured product component in the antibacterial layer (total solid content in the curable composition). .
In Table 1, the “Ag ion amount” column intends the silver ion amount per unit area measured in the extraction test.

表１に示すように、本発明の抗菌層付き基材は、短時間での抗菌性に優れると共に、耐光性にも優れていた。
一方、銀イオン量が所定の範囲より少ない比較例１〜２では、所望の抗菌性が得られず、銀イオン量が所定の範囲より多い比較例３では、耐光性が悪化した。 As shown in Table 1, the substrate with an antibacterial layer of the present invention was excellent in antibacterial properties in a short time and also in light resistance.
On the other hand, in Comparative Examples 1 and 2 in which the amount of silver ions was less than the predetermined range, the desired antibacterial property was not obtained, and in Comparative Example 3 in which the amount of silver ions was larger than the predetermined range, the light resistance was deteriorated.

１０ 抗菌層付き基材
１２ 基材
１４ 抗菌層 10 Base material with antibacterial layer 12 Base material 14 Antibacterial layer

Claims (10)

基材と、前記基材表面の少なくとも一部に配置された抗菌層とを有する、抗菌層付き基材であって、
前記抗菌層が、銀を含む抗菌剤を少なくとも１種含み、
前記抗菌層が親水性基を有するポリマーを含み、
前記親水性基がポリオキシアルキレン基を含み、
以下の抽出試験で測定される単位面積当たりの銀イオン量が１５〜５０ｎｇ／ｃｍ２である、抗菌層付き基材。
抽出試験では、ＪＩＳ Ｚ ２８０１：２０１０に規定された１／５００普通ブイヨン培地を抽出液として用い、前記抽出液の温度を３５±１℃に制御して、前記抗菌層付き基材中の前記抗菌層と前記抽出液とを１時間接触させ、前記抽出液に抽出された銀イオン量を測定し、得られた値を前記抗菌層の前記抽出液との接触面積で除して、単位面積当たりの銀イオン量を得る。前記銀イオン量の単位はｎｇであり、前記接触面積の単位はｃｍ２であり、前記単位面積当たりの銀イオン量の単位はｎｇ／ｃｍ２である。 A substrate with an antibacterial layer, comprising a substrate and an antibacterial layer disposed on at least a part of the surface of the substrate,
The antibacterial layer contains at least one antibacterial agent containing silver,
The antibacterial layer includes a polymer having a hydrophilic group,
The hydrophilic group includes a polyoxyalkylene group;
The base material with an antibacterial layer whose silver ion amount per unit area measured by the following extraction tests is 15-50 ng / cm < 2 >.
In the extraction test, 1/500 ordinary bouillon medium defined in JIS Z 2801: 2010 was used as the extract, and the temperature of the extract was controlled at 35 ± 1 ° C. The layer and the extract are brought into contact with each other for 1 hour, the amount of silver ions extracted in the extract is measured, and the obtained value is divided by the contact area of the antibacterial layer with the extract to obtain a per unit area. The amount of silver ions is obtained. The unit of the silver ion amount is ng, the unit of the contact area is cm 2 , and the unit of the silver ion amount per unit area is ng / cm 2 . 前記抗菌層の表面の水接触角が４０°以下である、請求項１に記載の抗菌層付き基材。   The substrate with an antibacterial layer according to claim 1, wherein a water contact angle on the surface of the antibacterial layer is 40 ° or less. 前記抗菌剤が、担体と、前記担体上に担持された銀とを含む銀担持担体である、請求項１または２に記載の抗菌層付き基材。   The base material with an antibacterial layer according to claim 1 or 2, wherein the antibacterial agent is a silver-carrying carrier containing a carrier and silver supported on the carrier. 前記抗菌層が、親水性基を有するモノマー、および、銀を含む抗菌剤を少なくとも有する硬化性組成物に硬化処理を施して形成され、前記親水性基を有するモノマー中の親水性基が、ポリオキシアルキレン基を含む、請求項１〜３のいずれか１項に記載の抗菌層付き基材。 The antibacterial layer is formed by performing a curing treatment on a curable composition having at least a monomer having a hydrophilic group and an antibacterial agent containing silver, and the hydrophilic group in the monomer having a hydrophilic group is The base material with an antibacterial layer according to any one of claims 1 to 3 , comprising an oxyalkylene group . 抗菌層付き基材を表面に有する、放射線撮影装置であって、
前記抗菌層付き基材が、基材と、前記基材表面の少なくとも一部に配置された抗菌層とを有し、
前記抗菌層が、銀を含む抗菌剤を少なくとも１種含み、
以下の抽出試験で測定される単位面積当たりの銀イオン量が１５〜５０ｎｇ／ｃｍ ２ である、放射線撮影装置。
抽出試験では、ＪＩＳ Ｚ ２８０１：２０１０に規定された１／５００普通ブイヨン培地を抽出液として用い、前記抽出液の温度を３５±１℃に制御して、前記抗菌層付き基材中の前記抗菌層と前記抽出液とを１時間接触させ、前記抽出液に抽出された銀イオン量を測定し、得られた値を前記抗菌層の前記抽出液との接触面積で除して、単位面積当たりの銀イオン量を得る。前記銀イオン量の単位はｎｇであり、前記接触面積の単位はｃｍ ２ であり、前記単位面積当たりの銀イオン量の単位はｎｇ／ｃｍ ２ である。 A radiographic apparatus having a substrate with an antibacterial layer on its surface,
The substrate with the antibacterial layer has a substrate and an antibacterial layer disposed on at least a part of the surface of the substrate,
The antibacterial layer contains at least one antibacterial agent containing silver,
A radiation imaging apparatus , wherein the amount of silver ions per unit area measured in the following extraction test is 15 to 50 ng / cm 2 .
In the extraction test, 1/500 ordinary bouillon medium defined in JIS Z 2801: 2010 was used as the extract, and the temperature of the extract was controlled at 35 ± 1 ° C. The layer and the extract are brought into contact with each other for 1 hour, the amount of silver ions extracted in the extract is measured, and the obtained value is divided by the contact area of the antibacterial layer with the extract to obtain a per unit area. The amount of silver ions is obtained. The unit of the silver ion amount is ng, the unit of the contact area is cm 2 , and the unit of the silver ion amount per unit area is ng / cm 2 . 抗菌層付き基材を表面に有する、タッチパネルであって、
前記抗菌層付き基材が、基材と、前記基材表面の少なくとも一部に配置された抗菌層とを有し、
前記抗菌層が、銀を含む抗菌剤を少なくとも１種含み、
以下の抽出試験で測定される単位面積当たりの銀イオン量が１５〜５０ｎｇ／ｃｍ ２ である、タッチパネル。
抽出試験では、ＪＩＳ Ｚ ２８０１：２０１０に規定された１／５００普通ブイヨン培地を抽出液として用い、前記抽出液の温度を３５±１℃に制御して、前記抗菌層付き基材中の前記抗菌層と前記抽出液とを１時間接触させ、前記抽出液に抽出された銀イオン量を測定し、得られた値を前記抗菌層の前記抽出液との接触面積で除して、単位面積当たりの銀イオン量を得る。前記銀イオン量の単位はｎｇであり、前記接触面積の単位はｃｍ ２ であり、前記単位面積当たりの銀イオン量の単位はｎｇ／ｃｍ ２ である。 A touch panel having a substrate with an antibacterial layer on its surface,
The substrate with the antibacterial layer has a substrate and an antibacterial layer disposed on at least a part of the surface of the substrate,
The antibacterial layer contains at least one antibacterial agent containing silver,
Silver ion per unit area measured by the following extraction test is 15~50ng / cm 2, a touch panel.
In the extraction test, 1/500 ordinary bouillon medium defined in JIS Z 2801: 2010 was used as the extract, and the temperature of the extract was controlled at 35 ± 1 ° C. The layer and the extract are brought into contact with each other for 1 hour, the amount of silver ions extracted in the extract is measured, and the obtained value is divided by the contact area of the antibacterial layer with the extract to obtain a per unit area. The amount of silver ions is obtained. The unit of the silver ion amount is ng, the unit of the contact area is cm 2 , and the unit of the silver ion amount per unit area is ng / cm 2 . 抗菌剤を含む抗菌シートであって、
前記抗菌剤が、銀を含む抗菌剤を少なくとも１種含み、
以下の抽出試験で測定される単位面積当たりの銀イオン量が１５〜５０ｎｇ／ｃｍ２であり、親水性基を有するポリマーを含み、前記親水性基がポリオキシアルキレン基を含む、抗菌シート。
抽出試験では、ＪＩＳ Ｚ ２８０１：２０１０に規定された１／５００普通ブイヨン培地を抽出液として用い、前記抽出液の温度を３５±１℃に制御して、前記抗菌シートと前記抽出液とを１時間接触させ、前記抽出液に抽出された銀イオン量を測定し、得られた値を前記抗菌シートの前記抽出液との接触面積で除して、単位面積当たりの銀イオン量を得る。前記銀イオン量の単位はｎｇであり、前記接触面積の単位はｃｍ２であり、前記単位面積当たりの銀イオン量の単位はｎｇ／ｃｍ２である。 An antibacterial sheet containing an antibacterial agent,
The antibacterial agent includes at least one antibacterial agent containing silver,
Silver ion content is 15~50ng / cm 2 der per unit area measured by the following extraction test is, comprises a polymer having a hydrophilic group, the hydrophilic group comprises a polyoxyalkylene group, an antibacterial sheet.
In the extraction test, 1/500 ordinary bouillon medium defined in JIS Z 2801: 2010 was used as the extract, and the temperature of the extract was controlled at 35 ± 1 ° C., and the antibacterial sheet and the extract were 1 The amount of silver ions extracted in the extract is measured for a period of time, and the obtained value is divided by the contact area of the antibacterial sheet with the extract to obtain the amount of silver ions per unit area. The unit of the silver ion amount is ng, the unit of the contact area is cm 2 , and the unit of the silver ion amount per unit area is ng / cm 2 . 表面の水接触角が４０°以下である、請求項７に記載の抗菌シート。 The antibacterial sheet according to claim 7 , wherein the water contact angle on the surface is 40 ° or less. 前記抗菌剤が、担体と、前記担体上に担持された銀とを含む銀担持担体である、請求項７または８に記載の抗菌シート。 The antibacterial sheet according to claim 7 or 8 , wherein the antibacterial agent is a silver-carrying carrier containing a carrier and silver supported on the carrier. 親水性基を有するモノマー、および、銀を含む抗菌剤を少なくとも有する硬化性組成物に硬化処理を施して形成され、前記親水性基を有するモノマー中の親水性基が、ポリオキシアルキレン基を含む、請求項７〜９のいずれか１項に記載の抗菌シート。 A curable composition having at least a monomer having a hydrophilic group and an antibacterial agent containing silver is subjected to a curing treatment, and the hydrophilic group in the monomer having a hydrophilic group is a polyoxyalkylene group. The antibacterial sheet according to any one of claims 7 to 9 , comprising:
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